全文获取类型
收费全文 | 1251篇 |
免费 | 38篇 |
国内免费 | 8篇 |
专业分类
化学 | 983篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 79篇 |
物理学 | 218篇 |
出版年
2023年 | 5篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 11篇 |
2016年 | 31篇 |
2015年 | 32篇 |
2014年 | 27篇 |
2013年 | 60篇 |
2012年 | 72篇 |
2011年 | 72篇 |
2010年 | 40篇 |
2009年 | 45篇 |
2008年 | 75篇 |
2007年 | 67篇 |
2006年 | 68篇 |
2005年 | 75篇 |
2004年 | 78篇 |
2003年 | 59篇 |
2002年 | 68篇 |
2001年 | 30篇 |
2000年 | 19篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 19篇 |
1993年 | 20篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 13篇 |
1982年 | 7篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 6篇 |
排序方式: 共有1297条查询结果,搜索用时 15 毫秒
71.
A validated LC‐MS/MS method for the determination of canagliflozin,a sodium–glucose co‐transporter 2 (SGLT‐2) inhibitor,in a lower volume of rat plasma: application to pharmacokinetic studies in rats
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Shinji Kobuchi Kyoka Yano Yukako Ito Toshiyuki Sakaeda 《Biomedical chromatography : BMC》2016,30(10):1549-1555
Canagliflozin is a novel, orally selective inhibitor of sodium‐dependent glucose co‐transporter‐2 (SGLT2) for the treatment of patients with type 2 diabetes mellitus. In this study, a validated liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method for the quantitative analysis of canagliflozin in a lower volume of rat plasma (0.1 mL) was established and applied to a pharmacokinetic study in rats. Following liquid–liquid extraction by tert‐butyl methyl ether, chromatographic separation of canagliflozin was performed on a Quicksorb ODS (2.1 mm i.d. × 150 mm, 5 µm size) using acetonitrile–0.1% formic acid (90:10, v/v) as the mobile phase at a flow rate of 0.2 mL/min. The detection was carried out using an API 3200 triple‐quadrupole mass spectrometer operating in the positive electrospray ionization mode. Selected ion monitoring transitions of m/z = 462.0 [M + NH4]+ → 191.0 for canagliflozin and m/z = 451.2 [M + H]+ → 71.0 for empagliflozin (internal standard) were obtained. The validation of the method was investigated, and it was found to be of sufficient specificity, accuracy and precision. Canagliflozin in rat plasma was stable under the analytical conditions used. This validated method was successfully applied to assess the pharmacokinetics of canagliflozin in rats using 0.1 mL rat plasma. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
72.
73.
Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Guo‐Ling Li Dr. Shinji Kanegawa Dr. Zi‐Shuo Yao Dr. Sheng‐Qun Su Shu‐Qi Wu Dr. You‐Gui Huang Dr. Soonchul Kang Prof. Dr. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17130-17135
Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H2O has a higher thermal relaxation temperature than that of 1A? 3H2O. 相似文献
74.
Syuji Fujii Shinji Yamashita Yuichi Kakigi Kodai Aono Sho Hamasaki Shin-ichi Yusa Yoshinobu Nakamura 《Colloid and polymer science》2013,291(5):1171-1180
Hydroxy-functional macrodisulfides have been synthesized by atom transfer radical polymerization of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in 2-propanol. Mean degrees of polymerization of the polymer chains beside the disulfide were fixed at 30, 60, and 90; since ATRP has reasonably good living character, the molecular weight distribution is relatively narrow. Furthermore, the macrodisulfides were reduced to synthesize corresponding thiol-terminated polymers with relatively narrow molecular weight distributions. 1H nuclear magnetic resonance and gel permeation chromatography were used to characterize the macrodisulfides and thiol-terminated polymers in terms of their chemical structure, molecular weight, and polydispersity, respectively. Dispersion polymerizations of styrene using the thiol-terminated hydroxy-functional polymers as a transtab (chain transfer agent + colloidal stabilizer) in ethanol resulted in colloidally stable submicrometer-sized polystyrene latex particles. Scanning electron microscopy, Fourier transform infrared spectroscopy, and elemental microanalysis were used to characterize the particles in terms of their morphologies, particle sizes and their distributions, and chemical compositions. 相似文献
75.
Shinji Nakaya Daisuke Segawa Toshikazu Kadota Yoshiaki Nagashima Tomoya Furuta 《Proceedings of the Combustion Institute》2011,33(2):2031-2038
The burning and sooting behaviors of isolated fuel droplets for ethanol and n-decane are examined in high concentration of the ambient carbon dioxide under microgravity. A quartz fiber with the diameter of 50 μm maintains the droplet in the center of the combustion chamber and the range in the initial droplet diameter is from 0.30 to 0.80 mm. The ambience consists of oxygen, nitrogen and carbon dioxide. The concentration of oxygen is 21% in volume, and that of carbon dioxide is varied from 0% to 60% in volume. Detail measurements of the projected image of the droplet are conducted by using a high speed video camera and the effective droplet diameter squared are calculated from the surface area of the rotating body of the projected object. From evolutions of the droplet diameter squared, the instantaneous burning rates are calculated. Time history of the instantaneous burning rate clearly represents the droplet combustion events, such as the initial thermal expansion, ignition and following combustion. The instantaneous burning rate for n-decane shows an increasing trend during combustion, while that for non-sooting ethanol remains almost constant or shows a decreasing trend. A slight stepwise increase in the instantaneous burning rate is observed for larger n-decane droplets in air, which may be attributed to soot accumulation. However, this behavior of the burning rate disappears in higher concentration of carbon dioxide. Direct observation of the droplet flame indicates suppression of soot production in higher concentration of carbon dioxide and the suppression is enhanced for smaller droplet. 相似文献
76.
77.
Abstract Several new polymers containing hydrophilic phosphatidylcholine analogues in the main chains and hydrophobic docosyl or stearyl groups in the side chains have been synthesized. The polymers exhibit thermotropic liquid crystalline behaviors from 65°C up to ca. 280°C as determined by polarizing microscopy. One of the polymers shows slight crystallinity as evidenced by wide-angle x-ray diffraction. The viscosity measurements show that some of the polymers have properties similar to usual polyelectrolytes. However, one polymer shows a linear increase of reduced viscosity. 相似文献
78.
Tatsuro Ouchi Kazuhiro Nomoto Yoshifumi Hosaka Minoru Imoto Tadao Nakaya Tsutomu Iwamoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6-7):859-866
Abstract Three kinds of betaine-type polymers, which are macromolecular amphoteric electrolytes, were found to be able to polymerize vinyl monomers in aqueous solution through a radical mechanism without any further initiator. Betain-type polymers form hydrophobic areas (HA) in water. Vinyl polymerization commenced in the HA. The effect of the pH of the aqueous solution on polymerization was investigated. 相似文献
79.
Using p,p'-dimethoxydiphenyldiazomethane (DMDM) as initiator, the polymerization of methyl methacrylate (MMA) in benzene or in bulk was carried out. The initial rate of polymerization, Rp, was found to be expressed by the following equation: Rp = k[DMDM]0.53 [MMA]0.84 The polymerization was confirmed to proceed by a radical mechanism. The over-all activation energy for the polymerization in benzene was calculated as 19.3 kcal/mole. The rate of thermal decomposition of DMDM was also measured in benzene and the rate equation was obtained as follows: kd (sec?1) = 1.0 × 1015 exp (?29.1 kcal/RT) (for 50-80°C) Explanations of these observations are discussed in connection with those of the preceding papers. 相似文献
80.
Abstract The binary system of tetramethyl tetrazene (TMT) and Co(II) chloride was used as initiator of acrylonitrile (AN) in dimethylformamide. The initial rate of polymerization (Rp) was found to be expressed by Rp = k[TMT]0.62[Co(II) chloride]0.57 [AN]2.00 The polymerization was confirmed to proceed via a radical mechanism. The over-all activation energy for the polymerization was estimated as 15.1 kcal/mole. On the basis of these results and the product analysis of the reaction between the catalyst components in the absence of monomer, the initiation mechanism of the polymerization is discussed. 相似文献